A cubic phase In4SnS4 nanomaterial, its preparation method and application

Abstract

The application belongs to the technical field of photocatalytic nanomaterials, and particularly relates to cubic phase In4SnS4 nanomaterial, a preparation method and application. The preparation method adopts the following steps: a soluble indium source, a tin source and a sulfur source are added into a high-boiling-point reaction medium to perform a solvothermal reaction, and a solid product after reaction is separated, so that the cubic phase In4SnS4 nanomaterial is obtained. The synthesis method has the advantages of simple process, low cost and mild reaction, and realizes controllable preparation of the cubic phase In4SnS4 nanomaterial with controllable size and morphology and high crystallinity. The cubic phase In4SnS4 nanomaterial synthesized by the method has a morphology of truncated cube, half-cube and / or octahedron structure, and the unique structure can provide a theoretical and experimental basis for developing related application researches such as catalysis, thermoelectricity and photoelectric conversion of crystal face engineering.

Description

Technical Field

[0001] This invention belongs to the field of novel nanomaterials technology, specifically relating to a cubic phase In4SnS4 nanomaterial, the preparation method of the material and its application in catalysis, thermoelectricity and optoelectronics. Background Technology

[0002] The information disclosed in this background section is intended only to enhance understanding of the overall background of the invention and is not necessarily to be construed as an admission or in any way implying that such information constitutes prior art known to those skilled in the art.

[0003] Exploring the relationship between material structure and properties is an important fundamental research topic in materials science. Among them, micro and nanomaterials, due to their unique structural advantages, have broad research and application prospects in fields such as clean energy development, environmental pollution control, and biomedicine.

[0004] Ternary In4SnS4 nanomaterials, as multifunctional materials with potential applications in thermoelectricity, optoelectronics, and catalysis, have attracted widespread attention from researchers in terms of their synthesis methods and the exploration of their structure-property relationships. Currently, reported methods for synthesizing In4SnS4 materials are limited to high-temperature solid-state methods. For example, in a high-temperature solid-state reaction, SnS and InS are first placed in a quartz tube, heated to 1050℃ under inert gas protection, and then cooled to 650℃ and annealed for 3 weeks to synthesize In4SnS4. However, this solid-state synthesis method is not only energy-intensive and time-consuming, but also results in uncontrollable product size and non-uniform morphology, which is detrimental to the large-scale preparation and micro / nano-integrated applications of In4SnS4 nanomaterials. Summary of the Invention

[0005] To address the aforementioned research background, this invention provides a method for preparing In4SnS4 nanomaterials, which simplifies the preparation process and provides milder reaction conditions compared to existing methods. To achieve the above objectives, this invention realizes the preparation of In4SnS4 nanomaterials based on a solvothermal reaction. The In4SnS4 nanomaterials prepared by this method exhibit controllable size and morphology, high crystallinity, and are cubic phase In4SnS4 nanomaterials. Furthermore, this invention investigates the photochemical conversion ability of the above-mentioned cubic phase In4SnS4 nanomaterials, demonstrating that these nanomaterials can achieve photocatalytic degradation of methylene blue, and hold promise for applications in the degradation of pollutants in aquatic environments.

[0006] Based on the above research results, the present invention provides the following technical solution:

[0007] In a first aspect, the present invention provides a cubic phase In4SnS4 nanomaterial, the XRD diffraction pattern of which is in 2... θCharacteristic peaks were observed at 12.1±0.2°, 17.5±0.2°, 21.6±0.2°, 24.9±0.2°, 25.8±0.2°, 27.1±0.2°, 28.2±0.2°, 29.8±0.2°, 30.6±0.2°, 32.5±0.2°, 33.1±0.2°, 36.1±0.2°, 39.1±0.2°, 42.1±0.2°, 44.2±0.2°, 45.2±0.2°, 46.5±0.2°, 47.3±0.2°, and 47.5±0.2°.

[0008] Furthermore, the present invention provides cubic phase In4SnS4 nanomaterials with different micromorphologies: truncated cubic, truncated half-cubic and / or octahedral structures, in a monodisperse state, with an edge length of 50~300nm.

[0009] Compared to existing In4SnS4 nanomaterial preparation processes, the preparation method provided by this invention can expose different crystal planes to form different polyhedra, thus providing a theoretical and experimental basis for developing applications related to crystal plane engineering.

[0010] Secondly, a method for preparing the cubic phase In4SnS4 nanomaterials described in the first aspect is provided, comprising the following steps:

[0011] A soluble indium source, tin source, and sulfur source are added to a high-boiling-point reaction medium for a solvothermal reaction, and the solid product after the reaction is separated to obtain the product.

[0012] The aforementioned soluble indium and tin sources include organic or inorganic acid salts containing indium or tin. Examples of feasible indium sources include indium acetylacetonate, indium trichloride, indium acetate, and / or indium bromide. Examples of feasible tin sources include triphenyltin chloride, diphenyltin dichloride, bis(acetylacetonate)tin dichloride, and / or tin iodide.

[0013] The soluble sulfur source is preferably an organic sulfide, including sulfur-containing alcohols, sulfur-containing acids or sulfur-containing ethers, such as thioglycolic acid, thiopropanol acid, n-dodecyl mercaptan, diphenyl disulfide and / or dibenzyl disulfide.

[0014] Referring to the ratio of the three elements in In4SnS4 nanomaterials, in a more effective embodiment, sulfur should be in appropriate excess, and the molar ratio of In:Sn:S in the indium source, tin source and sulfur source is 4:1:(4-8).

[0015] The high-boiling-point reaction medium is selected from one or more of organic amines, oleic acid, and octadecene. Optionally, the organic amine is selected from one or more of oleylamine, octadecylamine, or hexadecylamine. In a preferred embodiment of the present invention, the high-boiling-point reaction medium is a mixture of organic amine and oleic acid at a volume ratio of 1 to 7:1.

[0016] The solvothermal reaction method described above is as follows: Under oxygen-free and stirring-free conditions, indium, tin, and sulfur sources are added to a high-boiling-point reaction medium for continuous reaction. In the first stage, the temperature is raised to 100-160℃ and reacted for 30-90 minutes. In the second stage, the temperature is further raised to between 280-340℃, and the reaction time is controlled between 5-120 minutes. The purpose of the first stage reaction is to fully dissolve the indium, tin, and sulfur sources and remove oxygen, moisture, and low-boiling-point impurities from the reaction system. The second stage is the solvothermal reaction stage.

[0017] After the solvothermal reaction is complete, the solid product in the reaction solution can be separated by centrifugation or filtration. Then, the solid product is washed with cyclohexane and anhydrous ethanol in sequence to obtain the target product.

[0018] Thirdly, the cubic In4SnS4 nanomaterials described in the first aspect are provided for potential applications in catalysis, thermoelectricity, and optoelectronics.

[0019] Existing research indicates that In4SnS4 can be applied in the photovoltaic field. This invention also confirms that the cubic In4SnS4 nanomaterial possesses photocatalytic properties and can effectively degrade organic dyes such as methylene blue in the aquatic environment under light conditions.

[0020] Therefore, the applications described in the third aspect above include the application of the cubic In4SnS4 nanomaterials as photocatalytic degradation materials, and the application methods include, but are not limited to, any of the following:

[0021] (1) The cubic phase In4SnS4 nanomaterial is used to degrade organic dyes in aquatic environments;

[0022] (2) The cubic phase In4SnS4 nanomaterial is used to prepare a water environment purifier;

[0023] In the application of (1) above, the water environment includes natural environments such as rivers, lakes, and seas, as well as industrial and domestic water such as drinking water and sewage to be treated.

[0024] The organic dye is a dye that can be degraded under light conditions, including but not limited to methylene blue, methylene blue, and Sudan red; in one embodiment verified by the present invention, the dye is methylene blue.

[0025] The degradation method of organic dyes in the above-mentioned aquatic environment is as follows: the cubic phase In4SnS4 nanomaterial is dispersed into the water to be treated, and it is allowed to reach equilibrium. Xenon lamp irradiation is then applied for a period of time to achieve the degradation of organic dyes.

[0026] In aspect (1) or (2) above, the cubic phase In4SnS4 nanomaterial is preferably a surface-modified material. The purpose of the surface modification is to enhance its water solubility. The method of water solubility modification is as follows: the cubic phase In4SnS4 nanomaterial of the first aspect is dispersed in a mixture of cyclohexane and mercaptopropionic acid under ultrasonic action and left to stand. The solid part is separated and washed to obtain the final product.

[0027] In the above mixture, the volume ratio of cyclohexane to mercaptopropionic acid is 2~4:1, and the standing time is 20~25h.

[0028] Compared with the prior art, the beneficial effects of the present invention are:

[0029] 1. The cubic phase In4SnS4 nanomaterial provided by the present invention has nanoparticles that are monodisperse and do not stick together or aggregate. This monodispersity can maximize the exposure of surface active sites, improve the separation efficiency of photogenerated carriers, and significantly enhance the photocatalytic degradation ability.

[0030] Furthermore, the microstructure of the nanomaterials in this invention is not unique, including octahedral, truncated cubic, or truncated cubic structures, with slightly different dimensions. Since the octahedral structure preferentially exposes the {111} crystal facets, while the cubic structure dominates the {100} crystal facets, this invention effectively provides a variety of cubic phase In4SnS4 nanomaterials with different configurations and properties, which can meet the catalytic requirements of different fields.

[0031] 2. Compared with the existing high-temperature solid-state synthesis method, the present invention provides a method for preparing cubic phase In4SnS4 nanomaterials, which does not require excessively high heating temperatures and significantly shortens the reaction time.

[0032] Furthermore, the present invention can also achieve controllable preparation of cubic phase In4SnS4 nanomaterials with different microstructures as described above.

[0033] 3. Regarding the applications of In4SnS4 nanomaterials, existing research mainly focuses on photoelectric and thermoelectric conversion. This invention first demonstrates that the aforementioned cubic In4SnS4 nanomaterials possess strong absorption capacity in the visible-near-infrared light range and can effectively catalyze the photodegradation of organic dyes, improving degradation efficiency. Therefore, this invention also expands the photocatalytic applications of the aforementioned cubic In4SnS4 nanomaterials. Attached Figure Description

[0034] The accompanying drawings, which form part of this invention, are used to provide a further understanding of the invention. The illustrative embodiments of the invention and their descriptions are used to explain the invention and do not constitute an improper limitation of the invention.

[0035] Figure 1The X-ray diffraction (XRD) pattern of the target product in Example 1;

[0036] Figure 2 This is a scanning electron microscope (SEM) image of the target product in Example 1;

[0037] Figure 3 The UV-Vis-NIR absorption spectrum of the target product in Example 1 is shown below.

[0038] Figure 4 This is a graph showing the photocatalytic degradation of methylene blue by the target product in Example 1;

[0039] Figure 5 The X-ray diffraction (XRD) pattern of the target product in Example 2;

[0040] Figure 6 This is a scanning electron microscope (SEM) image of the target product in Example 3;

[0041] Figure 7 This is the X-ray diffraction (XRD) pattern of the target product in Example 4. Detailed Implementation

[0042] It should be noted that the following detailed description is illustrative and intended to provide further explanation of the invention. Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains.

[0043] It should be noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of exemplary embodiments according to the invention. As used herein, the singular form is intended to include the plural form as well, unless the context clearly indicates otherwise. Furthermore, it should be understood that when the terms "comprising" and / or "including" are used in this specification, they indicate the presence of features, steps, operations, devices, components, and / or combinations thereof.

[0044] In the context of this specification, the word "comprising" is considered to mean "especially including". It should not be interpreted as "consisting of only".

[0045] Terminology Explanation Section:

[0046] Microscopic morphology: The octahedral, i.e. cubic phase In4SnS4 nanomaterial described in this application, was observed to have the shape of nanoparticles by electron microscopy. Based on the different raw materials and preparation method parameters, the shape of the prepared nanoparticles is also different. Each type of cubic phase In4SnS4 nanomaterial usually has a certain shape as the main feature. For example, in octahedral nanomaterials, it can be considered that 90% or more of the nanoparticles are octahedral structures with uniform volume and shape, but there may still be a small amount of uncrystallized raw materials, cubic structures with similar structures, or irregular structures.

[0047] Octahedron: The octahedron described in this application has eight triangular faces, including regular octahedrons and rhombic octahedrons.

[0048] A truncated cube: Referring to the definition of an Archimedes polyhedron, it consists of 14 faces, including 8 triangles and 6 squares.

[0049] A truncated cube: Referring to the definition of an Archimedes polyhedron, it consists of 14 faces, including 8 triangles and 6 octagons.

[0050] To enable those skilled in the art to better understand the technical solution of the present invention, the technical solution of the present invention will be described in detail below with reference to specific embodiments.

[0051] Example 1

[0052] In this embodiment, a cubic phase In4SnS4 nanomaterial is provided, and its preparation method is as follows:

[0053] (1) Add 0.4 mmol of indium acetylacetonate, 0.1 mmol of triphenyltin chloride, 28 μL of thioglycolic acid, 7 mL of oleylamine and 1 mL of oleic acid to a 100 mL three-necked flask to obtain a mixture.

[0054] (2) Nitrogen gas is introduced into the three-necked flask in step (1), and the mixture is heated to 130°C and reacted for 60 minutes under magnetic stirring to remove water and low-boiling-point impurities from the reaction system.

[0055] (3) Continue heating the mixture to 340℃ and react at a constant temperature for 5 minutes. After the reaction is complete, cool to room temperature, centrifuge to separate the solid product in the reaction solution, and then wash the solid product three times with cyclohexane and anhydrous ethanol respectively. The obtained solid product is the target product.

[0056] Example 2

[0057] In this embodiment, a cubic phase In4SnS4 nanomaterial is provided, and its preparation method is as follows:

[0058] (1) Add 0.4 mmol indium trichloride, 0.1 mmol triphenyltin chloride, 35 μL thiopropanol acid, 7 mL oleylamine and 1 mL oleic acid to a 100 mL three-necked flask to obtain a mixture.

[0059] (2) Nitrogen gas is introduced into the three-necked flask in step (1), and the mixture is heated to 100°C and kept at a constant temperature for 90 min under magnetic stirring to remove water and low-boiling-point impurities from the reaction system.

[0060] (3) Continue heating the mixture to 320℃ and react at a constant temperature for 60 min. After the reaction is complete, cool to room temperature, centrifuge to separate the solid product in the reaction solution, and then wash the solid product three times with cyclohexane and anhydrous ethanol respectively. The obtained solid product is the target product.

[0061] Example 3

[0062] In this embodiment, a cubic phase In4SnS4 nanomaterial is provided, and its preparation method is as follows:

[0063] (1) In a 100 mL three-necked flask, add 0.4 mmol of indium acetylacetone, 0.1 mmol of bis(acetylacetone)tin chloride, 28 μL of thioglycolic acid, 6 mL of oleylamine and 2 mL of oleic acid to obtain a mixture.

[0064] (2) Nitrogen gas is introduced into the three-necked flask in step (1), and the mixture is heated to 130°C and reacted for 60 minutes under magnetic stirring to remove water and low-boiling-point impurities from the reaction system.

[0065] (3) Continue heating the mixture to 300℃ and react at a constant temperature for 90 min. After the reaction is complete, cool to room temperature and centrifuge to separate the solid product from the reaction solution. Then, wash the solid product three times with cyclohexane and anhydrous ethanol respectively. The obtained solid product is the target product.

[0066] Example 4

[0067] In this embodiment, a cubic phase In4SnS4 nanomaterial is provided, and its preparation method is as follows:

[0068] (1) In a 100 mL three-necked flask, add 0.4 mmol indium acetate, 0.1 mmol diphenyltin chloride, 0.4 mmol diphenyl disulfide, 5 mL octadecylamine, 1 mL oleic acid and 2 mL octadecene respectively to obtain a mixture.

[0069] (2) Nitrogen gas is introduced into the three-necked flask in step (1), and the mixture is heated to 130°C and reacted for 60 minutes under magnetic stirring to remove water and low-boiling-point impurities from the reaction system.

[0070] (3) Continue heating the mixture to 280℃ and react at a constant temperature for 120 min. After the reaction is complete, cool to room temperature, centrifuge to separate the solid product in the reaction solution, and then wash the solid product three times with cyclohexane and anhydrous ethanol respectively. The solid product obtained is the target product.

[0071] Example 5

[0072] In this embodiment, a cubic phase In4SnS4 nanomaterial is provided, and its preparation method is as follows:

[0073] (1) Add 0.4 mmol of indium acetylacetonate, 0.1 mmol of triphenyltin chloride, 28 μL of thioglycolic acid, 4 mL of oleylamine and 4 mL of oleic acid to a 100 mL three-necked flask to obtain a mixture.

[0074] (2) Nitrogen gas is introduced into the three-necked flask in step (1), and the mixture is heated to 160°C and kept at a constant temperature for 30 minutes under magnetic stirring to remove water and low-boiling-point impurities from the reaction system.

[0075] (3) Continue heating the mixture to 280℃ and react at a constant temperature for 120 min. After the reaction is complete, cool to room temperature, centrifuge to separate the solid product in the reaction solution, and then wash the solid product three times with cyclohexane and anhydrous ethanol respectively. The solid product obtained is the target product.

[0076] Composition, structure characterization and performance testing

[0077] Figure 1 The image shows the X-ray diffraction pattern of the target product obtained in Example 1. As can be seen from the figure, all diffraction peaks accurately represent the corresponding crystal planes in In4SnS4 (JCPDS Card No. 76-2015), and no other impurity peaks appear, indicating that the target product prepared in this example is a cubic In4SnS4 crystal. Similarly, Figure 5 , Figure 7 The results also showed that the target products prepared in Examples 2 and 4 had the same properties as... Figure 1 Similar results.

[0078] Figure 2 The image shown is a scanning electron microscope (SEM) image of the target product obtained in Example 1, indicating that the prepared In4SnS4 is a nanomaterial with an octahedral structure and an edge length of approximately 100-150 nm. Furthermore, Figure 6 The image shown is a scanning electron microscope (SEM) image of the target product obtained in Example 3, which shows that the prepared In4SnS4 is a nanomaterial with a truncated cubic structure and an edge length of about 200~300nm.

[0079] Figure 3The UV-Vis-NIR absorption spectrum of the product obtained in Example 1 demonstrates that the cubic In4SnS4 nano-octahedral material has strong absorption capacity in the visible-near infrared light range, indicating that the In4SnS4 nanomaterial can be used as a light-absorbing material in research fields such as photocatalysis and photoelectric conversion.

[0080] Figure 4 The results of photocatalytic degradation of methylene blue by the product obtained in Example 1 are shown. First, the cubic In4SnS4 octahedral nanomaterials were surface-modified with mercaptopropionic acid to enhance their water solubility. Specifically, the cubic In4SnS4 octahedral nanomaterials were dispersed under ultrasonication in a 3:1 volume ratio mixture of cyclohexane and mercaptopropionic acid, allowed to stand for 24 hours, and then washed three times with anhydrous ethanol by centrifugation. Next, 50 mg of the target product was weighed and dispersed in 50 mL of a 10 mg / L methylene blue aqueous solution, and stirred in the dark for 30 min to reach adsorption / desorption equilibrium. Then, the solution was irradiated with a 300W xenon lamp. Every 15 min, 0.5 mL of the mixed solution was centrifuged, and the supernatant was collected. The absorbance at 664 nm was measured using a UV-Vis spectrophotometer to calculate the degradation rate. Figure 4 As shown, after irradiation with a xenon lamp for 90 minutes, the In4SnS4 nanomaterials achieved a degradation rate of 79% for methylene blue, compared to only 10% in the blank experiment. These experimental results demonstrate that the In4SnS4 nanomaterials possess excellent photocatalytic degradation capabilities.

[0081] The cubic In4SnS4 nanomaterials obtained in Examples 2-5 above also have similar photocatalytic degradation effects as in Example 1.

[0082] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A cubic phase In4SnS4 nanomaterial, characterized in that, The nanomaterial has a cubic crystal phase and a microstructure of nanoscale polyhedra, exhibiting a monodisperse state, with the edge length of the polyhedra ranging from 50 to 300 nm. The preparation method of the cubic In4SnS4 nanomaterial is characterized by comprising the following steps: A soluble indium source, tin source, and sulfur source are added to a high-boiling-point reaction medium for a solvothermal reaction, and the solid product after the reaction is separated to obtain the product. The indium source is selected from indium acetylacetone, indium trichloride, indium acetate, and / or indium bromide; The tin source is selected from triphenyltin chloride, diphenyltin dichloride, bis(acetylacetone)tin dichloride and / or tin iodide; The sulfur source is selected from thioglycolic acid, thiopropanol acid, n-dodecyl mercaptan, diphenyl disulfide and / or dibenzyl disulfide; The In:Sn:S molar ratio in the indium source, tin source and sulfur source is 4:1:(4-8); The solvothermal reaction method is as follows: Under the condition of oxygen isolation and stirring, indium source, tin source and sulfur source are added to a high boiling point reaction medium for continuous reaction. In the first stage, the temperature is raised to 100~160℃ and reacted for 30~90min. In the second stage, the temperature is raised to 280~340℃ and the reaction time is controlled between 5~120min. The high-boiling-point reaction medium is a mixture of organic amine and oleic acid in a volume ratio of 1 to 7:

1.

2. The cubic phase In4SnS4 nanomaterial as described in claim 1, characterized in that, The XRD diffraction pattern of the nanomaterial is in 2 θ Characteristic peaks were observed at 12.1±0.2°, 17.5±0.2°, 21.6±0.2°, 24.9±0.2°, 25.8±0.2°, 27.1±0.2°, 28.2±0.2°, 29.8±0.2°, 30.6±0.2°, 32.5±0.2°, 33.1±0.2°, 36.1±0.2°, 39.1±0.2°, 42.1±0.2°, 44.2±0.2°, 45.2±0.2°, 46.5±0.2°, 47.3±0.2°, and 47.5±0.2°.

3. The cubic phase In4SnS4 nanomaterial as described in claim 1, characterized in that, The nanomaterial has a microstructure of truncated cube, truncated half cube, and / or octahedron; wherein the edge length of the octahedron is 100~150nm; and the edge length of the truncated half cube is 200~300nm.

4. The application of the cubic phase In4SnS4 nanomaterials according to any one of claims 1-3 in the fields of thermoelectricity, optoelectronics, and catalysis.

5. The application of the cubic phase In4SnS4 nanomaterial as described in claim 4 in the fields of thermoelectricity, photoelectricity, and catalysis, characterized in that, The application refers to the use of cubic In4SnS4 nanomaterials as photocatalytic degradation materials, and the application method is selected from any of the following: (1) The cubic phase In4SnS4 nanomaterial is used to degrade organic dyes in aquatic environments; (2) The cubic phase In4SnS4 nanomaterial is used to prepare a water environment purifier; The water environment is selected from natural water environments such as rivers, lakes, and seas, or industrial and domestic water. The organic dye is selected from methylene blue, methylene blue, or Sudan red.

6. The application of the cubic phase In4SnS4 nanomaterial as described in claim 5 in the fields of thermoelectricity, photoelectricity, and catalysis, characterized in that, The organic dye is methylene blue.

7. The application of the cubic phase In4SnS4 nanomaterial as described in claim 5 in the fields of thermoelectricity, photoelectricity, and catalysis, characterized in that, The degradation method of organic dyes in the aquatic environment is as follows: the cubic phase In4SnS4 nanomaterials are dispersed into the water to be treated and allowed to reach equilibrium. Xenon lamp irradiation is then applied for a period of time to achieve the degradation of organic dyes. In aspect (1) or (2), the cubic phase In4SnS4 nanomaterial is a surface-modified material, and the surface modification method is as follows: the cubic phase In4SnS4 nanomaterial of any one of claims 1-3 is dispersed in a mixture of cyclohexane and mercaptopropionic acid under ultrasonic action and left to stand, and the solid part is separated and washed to obtain the nanomaterial; in the mixture, the volume ratio of cyclohexane to mercaptopropionic acid is 2~4:1, and the standing time is 20~25h.

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